Process for the manufacture of water-insoluble dyestuffs and products obtained therefrom



The present invention concerns aprocess for Second method 7 the manufacture of water-insolubleazo dyestufis I f which consists in coupling in substance or upon N01 f 1 the fibre diazo or tetrazo-derivativesznot con- I 5 taining solubilising' groups such as COOH or v o s *f 0 5' 50 which reduced and rendered' cyclic by stannous CJE CsLi COINH I I 50 Patented Mar. 26, 1940 I I i I I I f I I UNITED'STIA'TES P TENT Q oFFIcE f PROCESS "FOR. THE MANUFACTURE OF WATER-INSOLUBLE DYESTUFFS AND PRODUCTS O BTAINED T HER' E F ROM I 1 Pierre Petitcolas; Rouen, I Re'n Goupil, ,St. I Etienne-du-Rouvray, and Joseph Frenkiel and n Rudolf Senti, Itouen, France, assignors. to Gompagnie Nationale de Matieres Colorantes et- Manufactures de Produits Chimiq'ues du Nord Reunies, Etablissements Kuhlmann No Drawing. Application July 2 0, 1938, Serial No. 220,332. In France July'27,*1937" '7 Claims. ((1260-1157) SOaH groups with acyl-jacetylated derivatives of heterocyclic bases of general formula:

c- Y 4 w Y in which either X represents an oxygen atom, and one Z, or one Y; or one Y and one Z, or one Z and W represent an NHz group or groups; or g, X represents .a sulphur-atom and one Z, or one Z and one Y, or one Z and W represent an NHz group or groups. In both cases the phenyl nuclei may be substituted by groups such as alkyl, alkoxy or aryloxy groups halogenatoms, orother substituents incapable of rendering the products water-soluble. I

Certain of the heterocyclic bases in question are i already known while others are prepared for the r 4 i first time andthere was used for this purpose, NO

for example one of the following methods. I r I In a general manner by reduction and cyclisa F rth m th d tion by means" of stannous chloride of an ,0-' Y I benzoyl-orthonitro-phenol or of an O-ben'zoyl-- orthonitro-thiophenol containing if desired other substituents, a Z-phenyl-benzoxazole in the first OHEICQNH case or a Z-phenyl-benzothiazole in the second 7 case is obtained. The introduction of the amino group or groups into these derivatives may take N 3 O place before or after the cyclisation; one may v for example start from an O-benzoyl-orthonitro- CHa.CO.NH s

phenol containing one or two supplementary nitro groups which will be reduced during the No a n 1 I cyclisation or one maynitrate and then reduce I r I I .VQHz.OO.NH sn- 8/ I I I a Z-phenyl-benzothiazole or one may start from an ortho-nitro-phenol containing an acylamino group which will be saponified after 'cyclisation.

Certain of the methods capable of being utilised for obtaining heterocyclic bases are formulated below.

4 ImII LI O cmooms.co First method 45 m chloride, gives:

I CQ I I I I II \C- I I I Q I NHj I e I '1 ENE '2) As has been indicated above the heterocyclic bases in question are according to the invention condensed with the acyl-acetic esters; as, acylacetic esters there may be employed such derivatives of the monoor polybasic acids as the acetyl-acetic esters, benZoyl-acetic esters, terephthaloyl acetic esters etc. i

The condensation between the acyl-acetic esters and the heterocyclic base may take place in the presence of a solvent for example chlorobenzene or in theabsence of such a solvent, or in the presence of an excess of ester thus acting as solvent, but preferably at elevated temperature.

, azodyestuffs.

The acyl-acetyl derivatives obtained are utilised according to the present invention as coupling components in the preparation of insoluble plicants have observed, in the form of alkaline salts, a very marked aflinity for cellulosic fibres,

They have in general, as the ap- The following examples of the carrying out of the invention are given in a non-limiting way.

Example 1 In the same conditions by utilising the 2-paminophenyl-benzoxazole, 2-p-acetoacetylaminophenyl-benzoxazole is obtained of melting point 195-200" C. with decomposition corresponding to the formula l With the 5-amino-2-p-aminophenyl-benzoxaZOle (M. P. 230 C.) there is obtained with acetylacetic ether as is indicated above, the 5-acetoacetylamino-2-p-acetoacetylamino-phenyl-benzoxazole in colourless needles (melting point 240 C.) which corresponds to the formula N omcoomoomao-O-rvncoomcocrn while the acyl-acetyl compounds of dehydrothioparatoluidine which has a constitution approximately as follows:

have practically no affinity and the acyl-acetyl derivatives of Z-aminobenzothiazole \CNH2 have a rather low afiinity.

This aifinity for cellulosic fibres renders the acylacetyl derivatives according to the invention particularly valuable for the preparation on the fibre of insoluble azodyestufis; By treatment of cellulosic fibres padded in alkaline solutions of these compounds by means of solutions of diazo compounds derived from bases not containing water-solubilising groups, veryvivid and very fast yellow shades may in fact be obtained.

The present invention is not, however, limited to this special process of obtaining dyestufis, it extends to the preparation of the dyestuffs upon the fibre by any known process for the preparation of dyestufis upon the fibre with the possible use of diazo-amino derivatives, nitroso-amines, Schiifs bases etc. as well as the manufacture of dyestuffs in substance.

3 grams of 5-acetoacetylamino-2-(p-acetoaoetylamino) -phenyl-benzoxazole are pasted with 6 cos. of ethyl alcohol, 2 cos. of soda solution of 34 B. and 3 cos. of water. It is diluted in 1 litre of water containing 15 grams of salt, 5 cos. of sodium sulphoricinate and 8 cos. of soda of 34 B.

Into this padding bath are introduced for half an hour grams of bleached cotton threads. The thread is expressed strongly and developed in a diazo bath containing per litre 3 grams of o-m'traniline 1n thestate ofdiazonium chlorozincate, 8 grams of A12(SO4)3 and 2 grams of glacial acetic acid. It is rinsed thoroughly and soaped at the boil for half an hour in a bath containing per litre 2 grams of Marseilles soap and 2 grams of sodium carbonate. A yellow gold colour is obtained having very good fastness properties.

By replacing the diazotised .o-nitraniline by diazotised dichloro-aniline-lflfi a vivid yellow is obtained. With diazotised o-chloraniline a vivid greenish yellow is obtained. If the padding bath is prepared with 2-p-acetoacetylamino-phenylbenzoxazole and if development is perfermed with diazotised ortho-nitraniline a vivid yellow is obtained.

Example 2 grams of 2-nitro-4-methyl-l-thiophenol m (prepared according to known methods starting from 4-methyl-2-nitro-1-chlorobenzene, by transformation to disulphidefollowed by partial reduction by glucose) are dissolved in 1600 cos. of

water and 126 cos. of caustic soda of 35 B.

With brisk agitation grams of benzoyl chloride are poured in. The benzoylatedderivative precipitates almost instantaneously. There are then added drop by drop 120 cos. of soda solution of 35 B. and the mixture is heated for half The crude product melts at 98-100 C.

an hour at50-60 C. The crystals are filtered and washed with water. Theyield'is about '70- 75%.

When

' recrystallised from alcohol it has the form of smallyellow crystals (M. P. 106 0.). v A reducing mixture is prepared with 300 grams of iron filings, 800 cos. of water and'30ccs. of

extracted with a solvent like chloroben'zene. The

solvent is removed with steam. The crystallised residue is constituted by 5-methyl-2-phenylbenzothiazole in an almost pure state (M. P.

145 C.). After recrystallisation from alcohol its melting point is 148 C. The reduction may likewise be carried out with zinc and dilute acetic acid or even with zinc and water in the presenceof chlorobenzene by starting the reduction with alittle acetic acid.

80 grams of '5-methyl-2-phenylbenzothiazole are pasted with 300 005. of sulphuric acid monohydrate and then '70 grams of mixed acid are poured in with 35 I-INOs, 1% water and 64% H2804. The mixture is heated for 4 hours at 60 C. and then, allowed to cool to ordinary temperature. The mass is poured upon ice. The crystals of nitratesderivatives are filtered andwashed in water and then, after-drying,purified by crystallisation in chlorobenzene (yellow crystals of melting point 240 C.) The 6-nitro-5-methyl-2- phenylbenzothiazole is reduced by Bechamps method. I

100 grams of iron powder are heated in 1000 cos. of water and 30 cos. of acetic acid. The nitrated derivative is introduced into this reducing mixture and the mixture is heated to' boiling for ten hours. After rendering the reduction mass alkaline there is extracted with cl1lo-robenzene.

220 C.) methyl-2-pheny1benzothiazole.

The yield is 60% starting from 5- When recrystallised from alcohol in which it dissolves with blue fluorescence the 5-methy1-6-amino-2-phenylbenzot-hiazole exhibits the form of needles which are almost colourless (M. P.'228 (1).,

grams of this base-are heated for ten minutes while distilling the alcohol formed in the reaction with 40 cos. of boiling acetylacetic ether (in the presence of a little sodium ethylate)., The product is allowed to crystallise by cooling tate in the same way the terephthaloyl aoetylbis (6-amin0-5-methyl-2-phenyl benzothiazole) is obtained.

The 6 aoetoacetylamino-5-rnethyl-2-phenyle benzothiazole is dissolved with the aid of ethyl alcohol andcaustic soda in 2. padding bath; and threads of cotton treated with this bath and then The solvent is removed with water vapour to isolate the base (M. P. approximately acid.

minutes and then the creamy white crystalline with a solution of the diazo' derivative of 2.5- dichloroaniline are dyed yellow golden shades of good fastness. i

,Eicample 3,

A solution of sodium disulphide in alcohol is made starting from 3l0 grams of NazSSHz O, 41 grams of S and 1300 cos. of ethyl alcohol. Little by littleto this solution are added 400 grams of 21.5-dichloro-1-acetylamino-lnitrobienzeue and then the product is heated on the water bath for one hour minutes. It is allowed to cool and then the disulphide crystals are filtered and taken up in 150 cos. of warm water to eliminate the mineral salts (yie ld=6.0%). The product obtained has a meltingpoint above 280" C.

-220 grams of this disulphide are pasted in 500 cos. of alcohol. 160 grams of glucose are added andh'eated on -a water bath for several hours- After cooling, 275 cos. of soda solution of B. is poured in little by little. There is rapidly obtained complete solution, the said solution being 1 dark red. The product is heated for '15 minutes on the water bath and then diluted with 2000 cos. of warm water- It isfiltered to eliminate certain impurities and poured in a thin stream into a solution of iced hydrochloric acid prepared with 500 cos. of HCl of 20 BQand 1000 grams of ice. The thiophenol precipitates in the form of a brownishsludge which is filtered,

1'70 grams of this compound are dissolved in 1000 cos. of water with the aid of 90 cos. of soda solution of 35 B. Into this solution are poured 125 grams of benzoyl chloride while cooling externally so that the temperature doesnot exceed 20 C. It is then mixed for 3 hours, then the temperature is raised to 70-80 C after it has been rendered alkaline with sodium carbonate.

' The crystals of the benzoyl derivative are filtered,

washed in hot waterand dried. After recrystallisation from ohlorobenzene the product exhibits the formfof clear yellow crystals (M. P.=16'7 C., yield about 80%).

' .100. grams of 1 ohloro-2-acetylamino-5-nitrofl-benzoylf-thiophenol are finely powdered and introduced intoa reducing mixture cooled to 10 C.-

and prepared with 1000 cos. of concentrated HCl and 400 grams of stannous chloride. It is allowed to mix for ten hoursin the cold. Then it is heated for one hour with gentle boiling. The orystals'are filtered and washed in water. They are taken up with 1000 cos. of water, 200 cos. of soda solution of 35 B. and grams of tartaric The product is heated to boiling for 15 melt is filtered and washed thoroughly. When recrystallisedfrom alcohol the 5-chloro-6-amino- 2-phenyl benzothiazole exhibits the form of fine straw-yellow needles (M. P. 180 0.). In alcoholic solution it shows a slight violet fluorescence.

Analysis Calculated Found Acetoacetylation is efiected as in the preceding example. When recrystallised from alcohol or chloro-benzene the 6-acetoacetylamino-5-chloro- Z-phenyl-benzothiazole exhibits the form of a white powder (M. P; 176 C.). p

3 grams of 6acetoacetylamino-5-chloro-2- phenylbenzothiazole are pasted with 6 cos. of denatured alcohol, 2 cos. of caustic soda of 34 B. and 6 cos. of cold water. If desired it is heated in order to dissolve it and the solution is poured into a litre of cold Water to whichhave previously been added 30 grams of common salt, cos. of sulphoricinate and 8 cos. of caustic soda of 34 B. Into this. padding bath are inserted for 30 minutes, 50 grams of bleached cotton thread. The thread is well dried and developed in a diazo bath containing per litre 3 grams of dichloroaniline 1.2.5. in the state of diazonium chlorozincate, grams of Al-2(SO4)3 and 2 cos. of acetic acid. It is well washed and soaped at the boil for half an hour in a bath containing per litre 2 grams of soap and 2 grams of sodium carbonate. A yellow shade is obtained having very good fastness properties.

By replacing the dichloroaniline by o-nitraniline or p-chloro-o-nitraniline very full yellows are obtained likewise having good fastness properties.

Example 4 A solution of sodium disulphide is prepared starting from 490 grams of Na2S.9I-IzO, 2000 cos. of ethyl alcohol and 66 grams of sulphur. The solution is added little by little to 680 grams of l acetylamino-Z-methoxynitro5-chlorobenzone in suspension in the cold in 1000 cos. of alcohol. The temperature rises itself and the disulphide commences to crystallise in fine clear yellow needles. The product is heated to boiling on the water bath for 1 hours then allowed to cool completely, filteredjand then washed thoroughly in water. The 3.3'-diacetylamino 4.4 dimethoxy 6.6-dinitro-1.1'-diphenyldisulphide formed is sparingly soluble in alcohol, a. little more in chlorobenzene from which it crystallises in clear yellow needles (melting. point above 280 C., yield about 80%).

330 grams of this disulphide are heated with 800 cos. of alcohol and 260 grams of glucose at 60 C. 450 cos. of soda solution of 35 B. is introduced in small portion with strong agitation. Complete solution is rapidly obtained, the solution being dark red. Heating is continued for a quarter of an hour on the water bath and the product poured into 1500 cos. of warm water. a light residue is filtered and the product is poured in a thin stream with good agitation into 500 cos. of H01 to which 1500 grams or" ice have been added. The crystals of thiophenol are filtered and washed in water. The crude product melts at 135 C. After purification from chlorobenzene it exhibits the form of golden yellow crystals (M. P. 140 C.=yield about 85%).

200 grams of the above thiophenol are dissolved in 2000 cos. of water and 90 cos. of the soda solution of 35 B. The product is filtered to eliminate a slight residue and after the addition of 26 grams of sodium carbonate it is cooled is maintained for an hour while testing for alkalinity'with swallow. The benzoylated derivative formed remains) crystalline. It is filtered in the hot and washed with water. When recrystallised from chlorobenzene the l-acetylamino 2-methoxye4-nitro-5 -benzoyl thiophenol gives almost colourless crystals (M. P.:183 C., yield about 85%) 300 grams of benzoylated derivative are finally comminuted and pasted in 300 ccs. of concentrated HCl. It is strongly agitated and into it are introduced little by little 1520 grams of stannous chloride while cooling externally with ice. It is allowed to mix for a day in the cold and then brought for 3 hours to 80 C. After cooling, it is filtered and washed in water. The crystals are taken up in 1000 ccsaof water, 200 cos. of soda solution of 35 B. and 50 grams of tartaric acid. The acetylated. derivative (M. P.:l90 C.) is filtered and Washed, which derivative corresponds to the formula:

It is saponified in 70% sulphuric acid. The product is heated until it has dissolved, poured upon ice and neutralised with soda. The base precipitates in the form of fine greenish yellow needles. When recrystallised from alcohol it melts at 151 C. Its acetoacetyl derivative is prepared as in the preceding example-M. 156 C. (from alcohol)- 3 grams of G-acetoacetyl-amino-5-methoxy-2- phenyl-benzothiazole are pasted in 6 cos. of denatured alcohol, 2 cos. of soda of 34 B. and 6 cos. of water. The product is heated to dissolve it and the solution is poured into 1000 cos. of water to which 5 cos. of sodium sulphorioinate and 8 cos. of soda of 34 B. have been previously added. Into, this padding bath are inserted for half an hour 50 grams of well boiled cotton thread. The thread is strongly pressed and developed in a diazo bath containing per litre 3 grams of dichloroaniline 1.2.5. in the state of diazonium chlorozincate, 10 grams of A12(SO4)3 and 2 cos. of glacial acetic acid. After washing and soaping as in the previous example, a golden yellow tint is obtained having very good fastness properties. By replacing the dia-zo derivative of dichloroaniline by that of o-chloroaniline, a greenish yellow shade is obtained.

Example 5 50 grams of 2-p-nitrophenylbenzothia-zole are dissolved in 500 grams of sulphuric acid of 66 B. The product is agitated while adding 120 grams of mixed acid with 33% of HNOIl, 68% of H2804, and 1% of H2O. The temperature rises to 65-70 C. It is maintained at this for an hour and the mass is then poured upon ice. The nitrated derivative is filtered and washed (dry weight=60 grams, M. P.=220-230 C.). By crystallisation from boiling acetic acid, fine needles which are very little coloured are isolated (M. P.=240 C.) whose analysis corresponds to the dinitro derivative 01 formula Nor ' chloroaniline 1.2.5.

It may be reduced in the following manner:

65 grams of 6-nitro-2-p'-nitrophenylbenzothiazole are pasted in 800 cos. of concentrated HCl and then 300 grams of stannous chloride are added. The product is heated to boiling for half an hour and then allowed to cool. By addition of alcohol the diamine hydrochlorate .is precipitated and is filtered and Washed with a little alcohol containing hydrogen chloride. The crystals are taken up in an excess of dilute caustic soda to which tartaric acid is added. The base is filtered thoroughly, washed with water and dried (weight 45 grams-M. P. 255 C.) ,By recrystallisation from chlorobenzene fine slightly yellow flakes are obtainedM.' P. 260 C. (n. 0.).

Analysis Found 30 grams of 6-amino-2-p'-aminophenylbenzothiazole are dissolved in cos. of acetyl acetic ether to which has been added 1 cc. of normal solution of sodium ethylate. The product is heated to boiling while distilling. the valcohol formed in the reaction. After a few minutes all diazotisable base has disappeared. The product is allowed to cool and the crystals are filtered and washed with ethyl alcohol to eliminate the acetylacetic ether used. The acetoacetylated derivative exhibits the form of large yellowish crystals readily soluble in dilute soda. The yield amounts to 80-85%.

1.5 grams of the above acetoacetylated derivative are pasted with 3 cos. of ethyl alcohol to which 1.5 cos. of soda solution of 35 B. have been added. The product is diluted with 5 cos. of hot water to obtain complete solution. This solution is poured into 1000 cos. of water to which have i been added 5 cos. of sodium sulphoricinate, 5 ccs. of soda solution of 35 B. and 15 grams of common salt.

In this padding bath is immersed for half an hour 50 grams of well boiled cotton thread. The thread is strongly pressed and developed in a diazo bath containing per 1itre'3 grams of di- (1=NI-I2) in the state of 'diazonium chlorozincate, 8 grams of aluminium sulphate and 5 cos. of glacial acetic acid. After half an hour it is thoroughly rinsed and soaped for twenty minutes at the boil in a bath containing per litre 2 grams of Marseille soap, 0.5 gram of sodium hydrosulphite and 0.5 cc. of soda of 35 B. There is thus obtained a very vivid yellow having very good fastness properties. By replacing the dichloraniline by o-chloroaniline, a vivid greenish yellow shade is obtained likewise having good fastness properties.

Example 6 grams of l.4-dichloro-2-acetylamino-5- nitrobenzene are dissolved 111300 ccs. of hot alcohol. This solution is poured into a solution of KHS prepared'by saturating with H25 a solution of 56 grams of KOH dissolved in 2000 cos. of ethyl alcohol and 60 cos. of water. The solution becomes deep red. It'is heated on the Water bath for some minutes; a sample diluted with water should leave behindno'precipitate. The alcoholic solution is pouredinto 9000 grams of ice,

1000 cos. of H20 and 200 cos. of concentrated HCl. The thiophenol precipitates. It melts at C. (chlo'robenzeneLT The thiophenol is filtered and utilised while still damp; it is dissolvedin the cold in 1000 cos. of 'water and 70 cc's.' of soda solution or 35 B. Smallquantities of impurities" are filtered and. with good agitation '95 grams'of p-nitrobenzoylchloride dissolved in cos. of chlorobenzene arepoured in, in the cold. 'After two hours of vigorous mixing the solution is completely decolourised. It is neutralised with a little "acetic acid, and then the solvent is removed with water vapour. The condensation product which separates in. the form of crystalline flakesis filtered,

washed and dried. r

50 grams of the above derivative are pasted in 500 cos. of concentratedhydrochloric acid.

350 grams of stannous chloride are added while mixing. The temperature rises by itself to 60 C.

At first complete dissolution is observed. .'At the NHz By condensationwith ethylbenzoylacetate the corresponding dibenzoylacetylated' derivative is obtained which is'utilised as substantive cornponent in dyeing by ice colours.

- Example 7 20 grams of 5-amino-2- p-aminophenyl-benzothiazole are dissolved at the boil in 100 cos. of acetyl acetic ether to which 1 cc. ofnormal solution of sodium ethylate are added. The product is heated for. some minutes while distilling the alcohol formed in the reaction until no diazotisable base remains. By cooling, the diazoacetylated derivative crystallises in the form of large crystals whichare filtered and washed in alcoholto eliminate the excess of acetylacetic.

ether. (Yield about 80%).

3 grams of this acetoacetylated derivative are pastedin 3 cos. of sodaisolution of 35 B. and 6 cos. of ethyl. alcohol. .The product is slightly heated and diluted with warm water until a clear solution is obtained. The volume is brought to a litre and 5 cos. of sodium sulphoricinate are The crystals are taken up in added, 15 grams ofcommon salt and '5 cos. of v soda solution of 35 B. 50 grams of well boiled cotton thread are placed for half an hour in this padding bath. After drying the product is developed in a diazo bath prepared as in Example 5 with the diazonium chlorozinca'te of dichloroaniline 1.2.5. By continuing the treatment as in Example 5 a yellow greenish shade is obtained of good fastness properties.

Example 8 400 grams of 2-nitro-4-methoxy-5-acetylaminothiophenol are dissolved in 1600 cos. of water to which have been added 170 cos. of soda solution of 35 Be. in the cold. A slight insoluble residue is filtered and then the product is cooled from outside with iced water. After having added grams of sodium carbonate dissolved in 200 cos. of water the product is violently agitated while pouring into it little by little asolution of 315 grams of p-nitrobenzoyl-chloride dissolved in 500 cos. of chlorobenzene. After two hours of mixing the product is heated to C. for half an hour. The product is allowed to cool and then the large crystals impregnated with chlorobenzene are separated. They are taken up in 500 cos. of chlorobenzene at 30-40" C., filtered and then washed with 500 cos. of cold ethyl alcohol. They are filtered and dried. The nitrobenzoylated derivative which corresponds to the formula is recrystallised from chlorobenzene; it exhibits then the form of yellow prisms (M. P.=208 C.).

133 grams of this derivative are pasted with 600 cos. of concentrated H01. 1200 grams of SI1C12 are added. After three hours of cold mixing the product is brought to the boil for two hours. After complete dissolution it is still left at that temperature for half an hour. After cooling, the product is diluted with 1000 cos. of Water and 500 grams of ice, then rendered alkaline with caustic soda until the tin oxide is redissolved. The base is filtered and washed with water. It exhibits the form of fine yellowish crystals which, when recrystallised from chlorobenzene form slightly brownish needles (M. P. 237 C.) corresponding to the formula The yield amounts to 65-70%.

20 grams of this diamine are introduced into 120 ccs. of acetylacetic ether to which 1 cc. of normal sodium ethylate solution have been added. The product is gradually heated to the boil while distilling the alcohol formed in the reaction. After a few minutes, diazotisable base is no longer found. By cooling, the diacetoacetylated derivative precipitates in fine crystals which are filtered and washed in alcohol. Purified with chlorobenzene the product melts at 210 C. The yield amounts to 90%.

1.5 grams of this diacetoacetylated derivative are pasted with cos. of soda solution of 35 B. and 5 cos. of ethyl alcohol. The product is diluted with hot water until it is completely dissolved and then it is brought to a volume of 1000 ccs. with cold water to which 5 ccs. of sulphoricinate and 15 grams of common salt have been added.

50 grams of well boiled cotton thread are immersed for half an hour in this padding bath. The thread is dried and the dyeing developed in a diazo bath prepared as in Examples 3 and 4 OHSO with dichloroaniline. The treatment is continued in the same conditions and a very fast golden yellow is obtained. By replacing the dichloroaniline by o chloroaniline, a vivid yellow is obtained likewise of good fastness.

Example 9 50 grams of 6-amino-2phenylbenzothiazole M. P.=198 C. (see Bogerth, Hugh, Blacke, Carbitt, CB 1926, II, 30 and CB 1927, II 700) are heated to boiling for some minutes in 80 cos. of acetyl acetic ether while distilling the alcohol formed. After prolonged cooling the acetoacetylated derivative formed is filtered. It exhibits the form of fine yellowish white needles which are washed in ether.

The dry weight is 30 grams and the melting point 157 C. 1

By replacing the acetylacetic ether by benzoylacetic ether the 6-benzoyl-acetylamino-Z-phenylbenzothiazole is prepared:

(M. P. 215 C. with decomposition).

70 grams of 6-amino-2-pheny1benzothiazole and 10 grams of the ethyl ether of terephthaloyl acetic acid are dissolved in 500 cos. of boiling chlorobenzene. A part of the boiled chlorobenzene is gradually distilled to remove the alcohol formed in the reaction. At first there is complete solution, but gradually the condensation product precipitates. After two hours the greenish yellow crystals (M. P. above 300 C.) are filtered which crystals probably correspond to the formula In the cooled filtrate of chlorobenzene one may isolate a yellow compound of melting point 201 C., which probably corresponds to the monocondensed compound.

6 grams of 6-acetoacetylamino-2-phenylbenzothiazole are pasted in 5 cos. of sodium sulphoricinate and 18 cos. of soda solution of 35 B. Upon this paste is poured 50 cos. of hot water. The product is diluted with cold water to bring the volume to 1 litre.

30 grams of bleached cotton thread are immersed in this bath for a quarter of an hour. The thread is strongly pressed and the dyeing developed in a diazo bath containing per litre in the state of diazonium chlorozincate, 4 grams of '1amino-2.5-dichlorobenzene, 15 grams of aluminium sulphate and 3 cos. of acetic acid. After rinsing in pure water and soaping at the boil for half an hour in a bath containing 2 grams of soap and 2 grams of sodium carbonate per litre, a full greenish yellow shade is obtained of good '2-nitro-4-amino-5-methoxy-tolu ,o-Chloranilme 5-nitro-2-amino-toluene and under pressure and to light. 7 Example 10 By utilizing the process described in Examnle 9 there is obtained 'startingir'om 5-Inetlioxy-6- amino-2-phenyl-benzoxazole" (M. P. 189 C.), 6-

acetoacetyl amino-5-inethoxy 2 --phenylbenzox-;:

azole (yellowish crystals M, P.= C.)

With 5-methyl-6-amino-Z-phenylbenzoxazOle (M. .P.=211 C.) the. 5-methyl-6-acetoacetyl-.

amino-2-phenylbenzoxazole isprepared of melting point 214 C. in the form of almost colourless flakes. .3 3 grams of 5-methoxye6-acetoacetylamino 25 phenylbenzoxazole are pasted in 3 ccsgof ethyl alcohol and 2 cos. of soda solution of 34 B. The product is diluted with 2 cos-of waterand the solution is poured into 500 cos. of Water to which H I cording to this invention combinationwith 5 cos. of sodium sulphoricinate and. i0 grams'of common salt have been added.- In thispadding obtained of good fastness properties.

bath are immersed for half an hour 20 grains an hour it is rinsed and then soaped for half. an.

.hour at the boil in a bath containingz grams'of -N2.2CO3 and 2 grams of soap per litre. After:

rinsing and drying a. full yellow orange Example 11- 152 grams of. ,m-nitro-p-toluidine are;diaz oi5 terials, etc.

The following tained by using certain couplingcomponents'ac certain diazo derivatives.

Dia'zo component I Coupling component S hade on cotton 4-el11o1o-2-amino-anisole 2-111ethoxy-4-benzoylamino-5-metl1yla1n1no-benzene 3-uitro-4-aminoanisole. 4-methoxy-4-aminodiphen Diamino-diphenylamine-azo-il-a ene. p-Chloro-o-nitranilin p-Nitraniline 3-nitro-4-amino-t 2'nitro-4-amino-L3-xylen 5-chloro-2amino-toluene 5-nitro-2- aminotoluene Alpha-aminoanthraqumone. 5-nitro-2-a1nmoanisole m-Chloranilineo-Nitraniline mNitraniline; 2-chloro-4-amino-toluene 2.5-dichloraniline 4-nitro-2-aminot0luene 4nitro-2-aminoanisole 4-chloro-2-amino-toll1ene 4-chloro-2-a,mino-anisole Z-methoxyl-benzoylammo-fi-methylaminobenzene. 3-nitro-4-aminoanisole 4'-methoxy-4-amino-diphenylamine Diamino-diphenylamine-azo 3-a.m1no- -me one. p-Ohloro-o-nitranllinen p-Nitraniline 3-nitro-4-amino-toluene 2-nitro-4-amino-L3-xylene 5-ch1oro-2-aminotoluene 2-nitro-4-amino-5-methcxytolu nc.

Alpha-aminoanthraquinone. 5-nitro-2-amino-an1'sole o-Ohloraniline m-Chloranilino.. o-Nitraniline....

fiacetoacetylamino-5-methoxy-2-p-aeetoacetyl-aminogphgnyl-benzothiazole. v

Reddish yellow.

-Viv id yellow. I

Brownish orange. Orange.

' Brown.

Bordeaux.

. Do. Reddish orange. Goldenyellow. Vivid yellow. Golden yellow.

DO; I. Reddish orange. Orange. 1 Vivid orange. I

Yellow- Do. Orange. Vivid orange. Brown.

Violet Bordeaux.

Brownish yellow. Yellow.

Orange yellow. Yellow.

mDo. 'Reddish yellow. Yellow.

Orange. Red shyollowr. Yellow.

' Do. Golden yellow. Yellow.

o. Goldenycllow Yellow.

Qrange'brown. Orange. I 'Reddish brown. Violet Bordeaux Orange yellow. Yellow. Orange Yellow. Yellow.

. vDo. Reddish yellow.

L vDo. Orange. eddish yellow. Greenish yellow.

-Do. Reddish'yellow.

. J20. lisable for" the colouration of paper, plastic matable imlicates thev shades obv v Diazo component Coupling component Shade on cotton m-Nitraniline 6- acetoeeetylamino -ehloro -2 p -aeetoaeetylamino Yellow.

phenyl-benzothiazole.

2-el1loro-1-arninotoluone. ..do. Do. 5 2.5-dichloraniline Greenish yellow. 4-nitro-2-amino-toluene Yellow. 4nitro-2-amino-anisole. Do. o -Chloraniline Vivid Greenish yellow.

m-Chloraniline Do. o-Nitraniline. Vivid orange. rn-Nitraniline Y low.

. 2-chloro-4-amino-t01l1ene. Vivid greenish yellow.

2.5diehloraniline Golden yellow. 4-nitro-2-amino-toluene. Yellow. 4-nitro-2-arninoonisole. Do.

p-C liloro-o-nitreniline Orange red. p-Nitraniline Reddisli yellow. 3nitro-4-amino- Orange. 1 2-nitro-4-emino-1" xylene Vivid greenish yellow. o-Ohloraniline y Do.

i emothiazole. m-Chloroniline cl Greenish yellow. o-Nitraniline Orange yellow. rn-Nitrnniline.. Yellow. 2-ehloro-4amino-toluene Greenish yellow.

V .2.5 diohloroniline Yellow.

4-nitro-2-emino-toluene... Vivid yellow. e-nitro-zarnino-anisolen. Reddisll yellow. p-Gl1loro-o-nil.raniline Orange brown. p-Nitraniline Reddish yellow. 3-nitro-4-arninortoluene... Orange. 2-nitro-4-amino l.3-xylene Vivid greenish yellow,

5-chloro-2-amino-tolueno Do.

2-nitro-4-e.mino-5-rnethoxy-toluene. Yellow. 5-nitro-2-amino-toluene Reddish yellow. Alpha-aminoanthraquinone.. Reddish orange. s-nitro-z-eminoanisol v Yellow. 4-ehloro-Zhmino-toluene. Golden yellow. 4-chloro-2aminoenisole Vivid greenish yellow. 2-methoxy-4-benzoylamino-5-methylam1nobenzene. Brownish yellow. 3-nitro-4-amino-anisole Vivid reddish orange. 4-rnethoxy-4-emino-diphenylamine. Bordeaux. Dieininodiphenylamine-azo-3-amino-4-methoxytolufine .do Violet Bordeaux. p-Chloro-o-nitraniline B-aeetoeeetylarnlno-2-phenyl-benzo-thmzole Orange yellow. o chloreniline o-ecetoacetylamin0-5-metl1y1-2-pl1Bnyl-bBn OXB 0 e Vivid yellow.

. 2.5diel1loraniline. d Golden yellow.

m-Chloreniline Greenish yellow. p-Ohloroo-nitraniline Orange. 4chloro-2 nmino-enisole Yellowish orange. Alphe-aminoonthraqumonm- Do. 4-ehloro-2-aminotoluene. Greenish yellow. 5-nitro-2-aminotoluene Orange. o-Chloreniline Yellow. 2.5-dichloraniline. Reddish yellow.

Yellow. p-Chloro-o-nitrani ine Yellowish orange. 4-chloro-2-amino-anisole Reddish yellow. A]pha-aminonnthraquinone Orange. 4-ohloro-2-erninotolnene Yellow. 5-nitro-2-amino-toluene... .....do Reddish yellow. 4-ehloro-2-emino-anisole 5 aeetoecetylemino 2 -p aeetoacetyl aminophenyl Vivid greenish yellow.

Alphaominoonthraquinone Orange. S-nitro-Z-eminoanisole Golden yellow. 3-nitro-4-aminoonisole Vivid orange. 4'-methoxy-4-on1inodiphenyl-emine Reddish brown. 2-iiethylsulphamidobenzoylumino-5-metl10Xy-8mln0' .do Vivid yellow.

enzene.

n-Aminodiphenylamine Brown. Diarninodiphenylamine-azo-3-amino-4-methoxy-tolnene. Reddish Bordeaux. p-Chloro-omitreniline Vivid golden yellow. p-Nitreniline Yellow. 3-nitro-4-aminotoluene. Vivid golden yellow. 2-nitro4-amino-l.3 xylene Vivid greenish yellow. 5-ch1oro-2-amino-tolnene Greenish yellow. 2-nitro4-amino-5-metboxy-toluene- Yellow. 5-nitro-2-amino-toluene Vivid yellow. o-Chloroniline Do. r m-Ohloraniline- Greenish yellow. o-Nitraniline.. Vivid yellow. rn-Nitraniline. Greenish yellow. 2-chloro-4-amino-tolnene. Do. 2. fi-diehloraniline Vivid reddish yellow. 4-nitro-2-amino-anisolo. Vivid golden yellow. 4-nitro-2-an1ino-toluene. Reddish yellow. p-Chloro-o-nitrnniline Vivid orange. p-Nitraniline Yellow. 3-nitro-4-amino-toluene... Yellow orange. 2-nitro-4-amino-1. 3xylene. Vivid greenish yellow. 5el1loro-2-amino-toluene. Do. 2-nitro-4-ainino-5-methoxy Yellow. 5-nitro-2-ainino-toluene Vivid golden yellow. 4'ehloro-2emino-toluene. Vivid greenish yellow. 4-diethylsulpl1an1ido-2ram Yellow. (:0 o-Arnino-azotoluene Orange. d-ehloro-Z-aminotoluene- Yellow. Z-methoxy-4-benzoylamino-fi-methylaminobenzene Vivid yellow. 4-ehloro-2-aminoanisole Alphe-aminoanthraquinone Orange. 5-nitro-2amino-anisole.. Vivid orange. 3-nitro-4-amino-enisole. Orange. 4'43BthOXY-l-flflllllOdiDhBllYlflH]lDG. Yellow brown. 2diethylsulphamido4-benzoylamino-5-n1ethoXy-aminobenzene Vivid yellow. 4-ernino-diphenylamine... Yellowish brown. Diamino-diphenylamine-azo-S-amino-4-methoxytoluene. Violet Bordeaux. o-Nitraniline Vivid greenish yellow. 6-nitro-2-emino-toluene. Vivid yellow. fi-chloro-zamino-toluene- Yellow. 7

Diazo component Coupling component Shade on cotton 2. 5-rliohlm'aniline E-chloro-6-acetoaeetylamino-2-phenyl-benzoxazole Orange yellow. p-Chloro-o-nitraniline do Yellow. Alpha-aminoanthraquinone do- Orange yellow. o-Nitraniline do Yellow. o-Nitraniline fi-acetoaeetylamino-2-phenylbenzothiazole Do. p-Ohloro-o-nitraniline. do Do. 5-ehloro-2-aminotoluene do D0. A1 ha-amino-anthraquinone d Orange yellow.

0- hloraniline m-Chloraniline o-Nitraniline m-Nitraniline 2-chloro-4-amino-toluene 2.5-dichloraniline 4-nitro-2-an1ino-anisole 4-nitro-2-amino-toluene p-Chloro-o-nitraniline. p-Nitraniline 3-nitro-4-amino-toluene 2mitro-4-amino-L3-xylene. 5-chloro-2-arnino-to1uene. 2-nitro-4-amino 5-meth0Xy-toluene 5-nitro-2-amino-toluene. 4-ehloro-2-amino-anisol Alpha-amino-anthraqm 5-nitro-2-an1ino-anisole 3-nitr0-4-amino-anisole 4'-methoxy-4-aminodiphe 4-ehloro-2-amino-toluene 4-diethylsulphamido2-amino-a o-Amino-azo-toluene. 6-ohloro-2-amino-toluene 2 methoxy 4-benzoylamin y enze Z-diethylsulphamido-4-benzoyl-amino-5-methoxy amino-benzene. 4-amino-diphenylamine Diamino -diphenylamine -azo- 3-amino-4-methoxytoluene. o-Ohloraniline In-Ohloraniline. o-Nitraniline m-Nitraniline. 2'chloro 4-arninoo uene 2.5-dicl1loraniline 4-nitro-2amino-anisole 4-nitro-2-arnino-toluene. 4-chloro-2-aminoanisole Alpha-amino-anthraquinone 5-nitro-2-amino-anisole. 3-nltro-4-amino-anisole 4-methoxy-4-aminodiphe p-Chloro-o-nitranilinep-Nitraniline 3-nitro-4-amino-tolnene 2-nitro-4-amino-L3-xylene 5-ehloro-2-amino-toluene 2-nitro-4-amjno-5-1nethoxy-toluene S-nitro-Z-amino-fnlneno 4-ch1oro-2-amino-toluene 4-diethylsulphamido-2-amino-anisole 2-p-acetoacetylamino-phenyl-benzoxazole o-Ohloraniline 5-chloro-fi-aceto-aeetylamino-2-phenyl-benzothiazole m-Chloraniline-. v

o-Nitraniline g m-Nitraniline 2-ehloro4-amino-toluene 2.5-dichlor nilin 4-nitro-2-amino-anisole 4-nitro-2-amino-tolnene p-Chloro-o-nifraniline p-Nitraniline. 3-nitro-4-aminoene 2-nitro-4-amino-L3-xylene 5-nitro-2-amino- 5-chloro-2-amino-toluene 2-n1tro-4-amino-5-methoxy-toluene 4-chloro-2'amino-tolnene 4-d1ethylsulphamido-2-amino-anisole o-Amino-azo-toluene 6-chloro-2-an1ino-toluene Z-methoxyA-benzoylamino-5-methyl-aminobenzene 4-chloro-2-aminoanisole Alpha-amino-anthraquinone 5-nitro-2-amino-anisole 3-nitro-4-amino-anisole'. 4n1ethoxy-4-aminodiphenylamine.. 2-d1etl1ylsulphamido+benzoy1amino-5-methoxy-aminobenzene.

o-Amino-diphenylarnine Diamino-diphenylarnine -n1ethoxytoluene o-Chloraniline m-Ohloraniline o-Nitraniline m-Nltraniline 2-chloro-4-amino-toluene.

2.5-dichloraniline 4-nitro-2-aminoanisole 4-nitro-2aminotoluene 4-chloro-2-an1ino-toluene d-diethylsulphamido-2-amino-aniso o-Amino-azo-loluene fi-aeetoarlzetylamino-2-p-aeetoacetylamino-phenyl-benzoxaz 6.

Vivid greenish yellow.

Greenish yellow. Yellow.

Do. Greenish yellow. Vivid yellow.

Vivid golden yellow.

0. Yellow.

R'eddish yellow. Vivid golden yellow. Vivid reddish yellow.

Brown orange.

Vivid greenish yellow.

- Vivid yellow.

Orange yellow. Greenish yellow. Vivid golden yellow. Vivid greenish yellow.

Orange brown.

Violet Bordeaux.

Vivid yellow.

ellow.

Golden yellow.

Greegish yellow.

Vivid yellow. Vivid golden yellow.

Vivid greenish yellow.

Greenish yellow. Yellow.

Vivid yellow.

Yellow.

Vivid greenish yellow. V1v d yellow.

vivlg golden yellow.

0. Golden yellow.

Vivid golden yellow.

Vivid greenish yellow. Golden yellow. Greenish yellow. Vividyellow.

Vivid greenish yellow. Yellow.

Vivid orange. Yell ow. Vivid golden yellow.

Vivid greenish yellow.

Orange yellow. Golden yellow. Reddish yellow. Reddish brown. Vivid greenish yellow.

Yellowish brown. Violet Bordeaux. Vivid greenish yellow.

Vivid yellow.

D0. Yellow.

.Greenish yellow.

Vivid yellow.

Diazo component Coupling component Shade on cotton o-Chloraniline Vivid greenish yellow. o-Nitraniline Orange yellow. 2.5-dicl110raniline Yellow. m-Nitraniline Orange yellow. Alphaaminoanthraquinone Orange. 4-chloro-2-aminotoluenc Yellow. m-Nitro-p-toluidine Orange yellow. m-Nitro-o-toluidinc Brown yellow. p-Nitro-o-anisidine Orange. ni-Nitro-p-anisidine..- Do. Tolidine Brown. 4-incthoxy-4-a1nino4liphcnylainine Reddish brown. o-Amino-azo-tolucne Brownish orange.

What we claim is: 1. The water insoluble azo-dyestufis having the general formula:

wherein X stands for a member of the group consisting of the alkyl and phenyl radicals and R for a residue of a member of the group consisting of the 6, 5, pand m-amino-Z-phenyl-benzoxazoles and the 6- and 5-amino-2-phenyh benzo-tl" azoles. and their substitution products by morn of the group consisting of the alkyl allroxy aryloxy groups and the halogen atoms.

2. The water insoluble azo-dyestufis having the general formula:

where X stands for a member of the group consisting of the alkyl and phenylradicals and R for a residue of a member of the group consisting of the 6, 5 pand m-amino-2-phenyl-benzonazoles and the 6- and 5-arnino-2-phenylbenzo-thiazoles, and their substitution products by members of the group consisting of the alkyl, alkoxy and aryloxy groups and the halogen atoms.

3. The water insoluble azo-dyestufis having the general formula:

4. Process for the manufacture of water-insoluble azodyestuifs which consists in coupling the diazo derivatives of amines not containing solubilising groups, with acylacetylated derivatives of heterocyclic bases being a member of the group consisting of the 6, 5, p and m-amino-2- phenylbenzoxazoles, the 6 and 5-amino-2-phenylbenzothiazoles, the G-amino, 5-amino-2baminophenyD-benzothiazoles and, benzoxazoles and their products of substitution by a member of the group consisting of the alkyl, alkoxy, aryloxy groups and the halogen atoms.

5. Process for the manufacture of water-insoluble azodyestuffs which consists in coupling the diazo derivatives of amines not containing solubilising groups, with acylacetylated derivatives of heterocyclic bases forming part of the group consisting of the 6, 5, p and m-amino-Z- phenylbenzoxazoles, the 6 and 5-amino-2-phenylbenzothiazoles, the S-amino, 5-amino-2(-aminophenyD-benzothiazoles and benzoxazoles, and containing alkyl groups incapable of rendering the products soluble in water. I

6. Process for the manufacture of water-in soluble azodyestufis which consists in coupling the diazo derivatives of amines not containing solubilising groups, with acylacetylated derivatives of heterocyclic bases forming part of the group consisting of the 6, 5, p and m-amino2 phenylbenzoxazoles, the 6 and 5-amino-2-phenylbenzothiazoles, the G-amino, 5-amino-2(-aminophenyD-benzothiazoles and benzoxazoles, and containing alkoxy groups incapable of rendering the products soluble in water.

'7. Process for the manufacture of water-insoluble azodyestuffs which consists in coupling the diazo derivatives of amines not containing solubilising groups, with acylacetylated derivatives of heterocyclic bases forming part of the group consisting of the 6, 5, p and m-amino-2- phenylbenzoxazoles, the 6 and 5-amino-2-phenylbenzothiazoles, the S-amino, 5-amino2(-aminophenyD-benzothiazoles and benzoxazoles, and containing halogen atoms incapable of rendering the products soluble in water.

PIERRE PETITCOLAS. RENE GOUPIL.

JOSEPH FRENKIEL. RUDOLF SEN'I'I. 

